Dynamics of direct H2O2 synthesis from H2 and O2 on a Pd nano-particle catalyst protected with polyvinylpyrrolidone

The kinetics of the H2–O2 reaction was studied on Pd–PVP (polyvinylpyrrolidone) nano-particles in water. With H+ and Br−, Pd–PVP catalyzed the H2O2 synthesis. H2 and O2 partial pressure dependencies revealed that the H2O2 formation followed the Langmuir–Hinshelwood mechanism and that the H2O2 selectivity varied greatly with pH2, which was quite different from the results using Pd/C. In the absence of Br−, the H2–O2 reaction primarily yielded H2O, and the reaction rate was very high and proportional to pH2. Br− adsorption measurements suggested that the proportion of highly unsaturated sites on Pd–PVP was much higher than on Pd/C. In the presence of H+ and Br−, the most unsaturated sites such as a corner site of the Pd particles would be blocked by the HBr adsorption and inert, and the major reaction would proceed on moderately unsaturated sites such as an edge site, which stabilize intermediates more than the least unsaturated sites such as a plane site.

Kinetics of the direct H2O2 synthesis from H2 and O2 and Br− adsorption behaviors on a Pd–PVP colloid catalyst in water containing H+ and Br− ions was quite different from those on a Pd/C catalyst, which proposed improved classification of Pd surface sites active for the H2O2 synthesis.Figure optionsDownload high-quality image (151 K)Download as PowerPoint slideHighlights
► Pd–PVP catalyzed H2O2 synthesis by L–H mechanism in the presence of H+ and Br−.
► Only H2O was produced in extraordinarily high rate in the absence of H+ and Br−.
► Br− adsorption measurement revealed that Pd–PVP was more unsaturated than Pd/C.
► Three types of Pd surface sites were proposed according to the degree of unsaturation.